"A POLYALCYCLIC COMPOUND"

Abstract

The present invention provides polyalkylcyclic compounds of general formula (I) having the structure: The present invention also provides process for preparing the compound of formula

Full Text

Field cf the Invention
The present invention relates to new chemical entities and the incorporation and use of the new chemical entities as fragrance chemicals. Background of the Invention
US Patent Numbers 5,227,367; 5,733,866; and 5,665,698 hereby incorporated by reference as iset forth in their entirety disclose polycyclic chemicals that are suitable for uss as ftagrance chemicals. Those with slkil in the art appreciate how differences in the chemical structure of the molecule can result in significant differences in the odor, notes and characteristics of a molecule. These variations and the ongoing need to discover and use the new chemicals in the development of new fragrances allows perfumers to apply the new compounds in creating new fragrances. Summary of the Invention
The present invention provides novel chemicals, and the use of the chemicals to enhance the fragrance of perfumes, toilet waters, colognes, personal products and the like. In addition, the present invention is directed to the use of the novel chemicals to enhance fragrance in perfumes, toilet waters, colognes, personal products and the like.
More specifically, the present invention is directed to the novel compounds, represented by the structure of Formula I set forth below:
(Formula Removed)
Another embodiment of the invention is a method for enhancing a fragrance by incorporating an olfactory acceptable amount of the compound provided above.
These and other embodiments of the present invention will be apparent by reading the following specification. Detailed Description of the Invention
The novel compounds of the present invention are more fully described by the following structures:
(Formula Removed)
where X, A, and B are as described above.
Those with skill in the art will appreciate that the dotted line represents a single or double bond. In a preferred embodiment the molecule does not contain a double bond. In a highly preferred embodiment the molecules contain the ring structure without the double bond and m=0. These molecules are represented by the following structure:
(Formula Removed)
w here A, B and X have the definition set forth above. In a preferred embodiment of the invention the compounds have the following structure

(Formula Removed)

Most preferably M=0 and R and R’ are independently selected from H and CH3.
Highly preferred embodiments of the invention are the following compounds wherein the substituents have the following values when applied to the compound of Formula I
(Table Removed)

Embodiments of the invention.
One embodiment of the invention provides a process for the preparation of compounds of general formula (I), the said process comprising the steps of:
(Formula Removed)
wherein dotted lines optionally represents a part of the double bond; M = 0 or 1; A = O; B is CH3C(=CH2)CH2-,CH2=CHCH2-,BrCH2CH2- or BrCH(CH3)CH2;. A and B together is -CH2C(RR')-O-(R and R' are independently represented by H or CH3) and X is also independently represented by H or CH3, the said process comprising the steps of: (b) reacting a compound of general formula (II) by stirring with lithium di-isopropyl
amide and at a temperature range of -10°C to ambient temperature in an organic
solvent for a period of 2-4 hours,
(Formula Removed)
wherein dotted line M and X have the same definition mentioned above; treating the reaction mixture of step (a) with HMPA, optionally sodium iodide and substituted or unsubstituted unsaturated alkyl halide or saturated 1,2-dihaloalkane at an ambient temperature to reflux temperature for a period of 8-24 hrs. to obtain compounds of formula (III)
(Formula Removed)
wherein dotted line, B, M and X have the same definition as mentioned above; (c) reducing the compound of formula (III) of step (b) with Vitride or RED-AL in toluene at a temperature range of 60° - 100°C for a period of 1 to 4 hours to obtain compound of formula (IV)
(Formula Removed)
wherein dotted line, B, M and X have the same definition as mentioned above; (d) treating the compound of step (c) of formula [IV, B = CH3C(=CH2)CH2-] with methanesulphonic acid, in an organic solvent at a temperature range of ambient to 90°C for a period of 15-24 hrs. or formula [IV, B=BrCH2CH2-] with sodium hydride in an organic solvent at reflux temperature for a period of 6-10 hrs to obtain compounds of formula (IA)
(Formula Removed)

wherein dotted line, M, R, R' and X represent the same definition as mentioned above;
(h) obtaining compound of formula (I) also by reacting compound of formula (V) with substituted or unsaturated alkylhalide or saturated 1,2-dihaloalkane in presence of alkaline metal oxide in corresponding alcoholic solvent at a temperature range of 30°-50°C for a period of 20-24 hours to obtain a compound of formula (VI)
(Formula Removed)
wwherein M, R and X have the same definition as mentioned earlier; subjecting the compound of formula (VI) of step (e) to Claisem's rearrangement with Prinol (EXXcn) around 180°-200°C for 10-16 hours to obtain compound of formula
(Formula Removed)

(i)

wherein M, X and R have the same definition as mentioned above; treating compound of formula (VII) of step (0 with p-toulene sulphonic acid in an organic solvent at a temperalure range of 80 ° to 90° C to obtain compound of formula (VIII)

(Formula Removed)

wherein M, X and R have the same definition as mentioned earlier; and (h) hydrogenating compound of formula (VIII) of step (g) to obtain compound of formula (IA) wherein R' = H.
An embodiment of the invention relates to a process, wherein compounds of formula II to IV are
obtained by performing steps (a) to (c).
Another embodiment of the invention, the compounds of formula (V) to (VIII) are obtained by performing steps (e) to (g).
Still another embodiment of the invention, the organic solvent used in step (a) is selected from group consisting of diethylether, tetrahydrofuran or toluene and preferably tetrahydrofuran.
Still another embodiment of the invention, substituted and unsubstituted unsaturated alkyl halide used wherein in step (b) is selected from allyl chloride, allyl bromide, 2-methylalkylchloride or 2-methyIallylbromide.
Yet another embodiment of the invention, saturated 1,2-dihaloalkane used in step (b) is selected
from dichloroethane, dibromoethane, diiodoethane, 1-methyldichloroethane, 1-
methyldibromoethane, 1-methyldiiodoethane and preferably dibromoethane or 1-
methyldibromoethane.
Yet another embodiment of the invention, the organic solvent used in step (d) is selected from
toluene, 1-nitropropane or tetrahydrofuran.
(Formula Removed)
Yet another embodiment of the invention, the alkalimetaloxide used in step (e) is selected from sodiummethoxide, sodium ethoxide, sodium isopropoxide and the alcoholic solvent selected from methanol, ethanol or isopropanol.
Still another embodiment of the invention, substituted and unsubstituted the unsaturated alkyl halide used in step (e) is selected from allyl chloride, allyl bromide, 2-methylalkylchloride or 2-methylallylbromide.
Still another embodiment, the saturated 1,2-dihaloalkane used in step (e) is selected from dichloroethane, dibromoethane, diiodoethane, 1-methyldichloroethane, 1-methyldibromoethane, 1-methyldiiodoethane and preferably dibromoethane or 1-methyldibromoethane.
Still another embodiment relates to a process wherein in step (h) the hydrogenating agent used is selected from the metal catalysts of rhodium or platinum.
One more embodiment of the invention relates to a synergistic composition for enhancing or
modifying the odor properties of a fragrance by incorporating an olfactory acceptable amount of
compounds of formula (I).
Another embodiment of the invention relates to a synergistic composition, wherein the fragrance
is incorporated into a product selected from perfumes, cologne, toilet waters, personal care
products, cleaning products, and air freshners.
Still another embodiment relates to a synergistic composition, wherein the claimed product is
selected from a group consisting of detergents, dishwashing composition, scrubbing compounds,
and window cleaners.
Yet another embodiment of the invention provides a synergistic composition, wherein the
compound of formula (I) used is selected from group consisting of 4,10, 10, 11, 12,12-
hexamethyl-3-oxatricyclo [7.3.0.0]dodecane, 4,4,10,10,11,12,12-heptamethyl-3-
oxatricyclo[7.3.0.0]dodecane.
(Formula Removed)

The novel compounds of the present invention are prepared by one of several reaction sequences set forth below. The compounds of Examples 1, 2, 3, 8, 9, 10, 12, 13, and 14, set forth below, were prepared by the sequence:
(sequence Removed)
The reaction sequence set forth above is summarized by the following reactions.
The first reaction is a three (3) carbon addition via allyl alcohol Claisen rearrangement or carbon alkylation with methallyl chloride. This reaction (Claisen rearrangement) is typically conducted at a temperature of from about 150 to about 250 °C. In a preferred embodiment the reaction is catalyzed using an acid catalyst, preferably methanesulfonic acid or para toluenesulfonic acid. The carbon addition reaction is then followed by an aluminum hydride ketone reduction reaction. The ketone is reduced to form the corresponding alcohol. The final reaction set forth above is an acid catalyzed ether formation that is conducted at a temperature of from about 70 to about 130 °C. This reaction is usually conducted in a solvent such as xylene or toluene with toluene being the preferred solvent.
The compounds of Examples 5-7 were prepared by the following general sequence:
(sequence Removed)
The first reaction is a carbon alkylation employing either allyl chloride or methallyl chloride depending if the desired R group is H or CEj. This reaction is typically conducted at a temperature of from about 23 to about 100 °C. The reaction is usually conducted with a base catalyst employing sodium methoxide or sodium hydroxide. The next reaction is a thermal Claisen rearrangement conducted at a temperature of from about 170 to about

250 °C. The third reaction is an acid catalyzed ether formation employing similar temperatures and catalysts as described above, followed by a catalytic hydrogenation employing rhodium or platinum as a catalyst.
The compounds of Examples 4 and 11 are prepared by the sequence:
(Formula Removed)
wherein the reaction is a three (3) carbon addition via allyl alcohol Claisan rearrangement or carbon alkylation with methallyl chloride using the conditions and catalysts described above.
The starting materials when M=0 for the above described reaction can be found in US Patent Numbers 5,227,367, 5,733,866 and 5,665,698. Similarly, the starting materials for the above materials when M=l can be found in US Patent 3,927,083, hereby incorporated by reference, German patent 2330648 and Japanese patent 09249584.
Those with skill in the art will recognize that the compounds of the present invention have several chiral centers, thereby providing numerous isomers of the claimed compounds. As used herein the compounds described herein include the isomeric mixtures of the compounds as well as those isomers that may be separated using techniques known to
those with skill in the art. Suitable techniques include chromatography, particlularly gel chromatography.
The optical isomers for the compound 4, 10, 10, 11, 12, 12-hexamethyl-3-oxatricyclo[7.3.0.0]dodecane are provided in the following table. One with skill in the art would be able to formulate fragrance compositions using one or more or the following isomers and mixtures of the isomers:

(Table Removed)
The compounds of the present invention have a powerful amber fragrance, with soft, woody notes.
The use of the compounds of the present invention is widely applicable in current perfumery products, including the preparation of perfumes and colognes, the perfuming of personal care products such as soaps, shower gels, and hair care products as well as air fresheners and cosmetic preparations. The present invention can also be used to perfume
cleaning agents, such as, but not limited to detergents, dishwashing materials, scrubbing compositions, window cleaners and the like.
In these preparations, the compounds of the present invention can be used alone or in combination with other perfuming compositions, solvents, adjuvants and the like. The nature and variety of the other ingredients that can also be employed are known to those with skill in the art.
Many types of fragrances can be employed in the present invention, the only limitation being the compatibility with the other components being employed. Suitable fragrances include but are not limited to fruits such as almond, apple, cherry, grape, pear, pineapple, orange, strawberry, raspberry; musk, flower scents such as lavender-like, rose-like, iris-like, carnation-like. Other pleasant scents include herbal and woodland scents derived from pine, spruce and other forest smells. Fragrances may also be derived from various oils, such as essential oils, or from plant materials such as peppermint, spearmint and the like.
A list of suitable fragrances is provided in US Pat. No. 4,534,891, the contents of which are incorporated by reference as if set forth in its entirety. Another source of suitable fragrances is found in Perfumes. Cosmetics and Soaps. Second Edition, edited by W. A. Poucher, 1959. Among the fragrances provided in this treatise are acacia, cassie, chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cut hay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose, vanilla, violet, wallflower, and the like.
Olfactory effective amount is understood to mean the amount of compound in perfume compositions the individual component will contribute to its particular olfactory characteristics, but the olfactory effect of the perfume composition will be the sum of the effects of each of the perfumes or fragrance ingredients. Thus the compounds of the invention can be used to alter the aroma characteristics of the perfume composition, or by modifying the olfactory reaction contributed by another ingredient in the composition. The amount will vary depending on many factors including other ingredients, their relative amounts and the effect that is desired.
The level of compound of the invention employed in the fragranced article varies from about 0.005 to about 10 weight percent, preferably from about 0.5 to about 8 and most preferably from about 1 to about 7 weight percent. In addition to the compounds other agents can be used in conjunction with the fragrance. Well known materials such as surfactants, emulsifiers, polymers to encapsulate the fragrance can also be employed without departing from the scope of the present invention.
Another method of reporting the level of the compounds of the invention in the perfumed composition, i.e., the compounds as a weight percentage of the materials added to impart the desired fragrance. The compounds of the invention can range widely from 0.005 to about 70 weight percent of the perfumed composition, preferably from about 0.1 to about 50 and most preferably from about 0.2 to about 25 weight percent. Those with skill in the art will be able to employ the desired level of the compounds of the invention to provide the desired fragrance and intensity.
The following are provided as specific embodiments of the present invention. Other modifications of this invention will be readily apparent to those skilled in the art. Such modifications are understood to be within the scope of this invention. As used herein all percentages are weight percent unless otherwise noted, ppm is understood to mean parts per million; mm is understood to be millimeters, ml is understood to be milliliters, Bp is understood to be boiling point, THF is understood to be tetrahydrofuran, Hg is understood to be mercury and g is understood to be grams. IFF as used in the examples is understood to mean International Flavors & Fragrances Inc., Hazlet, NJ, USA.

Example 1
Preparation of 7,7,8.9.9-pentamethvl-3-prop-2-enylbicvcIof4.3.01nonan-2-one
The synthesis of the starting material for this example is set forth in US Patent Nos. 5,227,367 , US 5,733,866, US 5,665,698.
A 3 liter flask equipped with a vigreux column and a distillation head was charged with 624g (3 mole) of 7J7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one, 435g (7.5 mole) allyl alcohol, 97g (1.6 mole) acetic acid, and 15g (0.16 mole) methanesulfonic acid. The mixture was heated to 80-85°C. Trimethyl orthoformate 350g (3.3 mole) was added over 24 hours with removal of lights (methanol) atmospherically. The reaction mass was heated to 180 °C with removal of lights and aged at 180°C for 2hr. The crude reaction mass was cooled and 800ml of water and 400ml of toluene was added. The aqueous layer was discarded and the organic layer was washed with brine.
The crude organic layer was distilled to recover toluene as well as 285g of 7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-one as a mixture of isomers (Bp 106°C at ImmHg).
The nmr spectrum of 7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-one is as follows: 0.68-1.13 ppm (ms, 15H), 1.34-1.63 ppm (m, 5H), 1.77-2.50 ppm (m, 4H), 4.93 ppm (m, 2H), 5.74 ppm (m, 1H)
Example 2
Preparation of 7.7.8.9.9-pentamethvI-3-prop-2-envlbicvclo f4.3.01 nonan-2-o!
A mixture of VITRIDE® (Zeeland Chemicals) 70% in toluene, 338g (1.17 mole) and toluene (732ml) was heated to 100°C. 7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-one, 290g (1.17 mole) was added over 2hrs. The excess VITRIDE® was neutralized with 2-propanol (105g) and the reaction mass was quenched with aqueous sodium hydroxide (280g of 50% NaOH). The lower aqueous layer was discarded and the organic layer was washed with brine.
The organic layer was distilled to recover toluene, as well as 163g of 7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-ol as a mixture of isomers (Bp 128-130° at 3 mmHg).
The nmr spectrum of 7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-ol is as follows: 0-59-1.02 ppm (ms, 15H), 1.14-1.58 ppm (m, 5H), 1.66-2.53 ppm (m, 4H), 3.25-3.87 ppm (dd, IH), 3.93-4.05 ppm (bs, IH), 4.98-5.11 ppm (m, 2H), 5.70-5.94 ppm (m, IH).
Example 3
Preparation of 4.10J0.11.12.12-hexamethvl-3-oxatricvcIof7.3.Q.O1dodecane
A mixture of 7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-ol, 163g (0.65 mole), toluene 163g and methanesulfonic acid 11.5g (0.11 mole) was heated to 80-90°C. The reaction mass was aged for 24 hours then cooled to room temperature. The reaction was quenched with 10% aqueous sodium carbonate solution (50 ml). The organic layer was washed twice with 10% aqueous sodium carbonate solution (50 ml) then brine.
The organic layer was distilled to recover toluene as well as 112g of 4,10,10,11,12,12-hexamethyl-3-oxatricyclo[7.3.0.0]dodecane as a mixture of isomers (Bp 95°C at 2 mm Hg).

Example 7
Preparation of 2.6.6J.8.8-hexamethvl-2.3-dihvdroindanor4,5-blfuran
A mixture of l,l,2,3,3-pentamethyl-5-prop-2-enylindan-4-ol 38g (0.15 mole), toluene 100 ml and p-toluenesulfonic acid (ptsa) 2.3g (0.01 mole) was heated to 80-90°C for 15 hours. The reaction mass was cooled to room temperature and quenched with 10% aqueous sodium carbonate (100 ml). The aqueous layer was discarded and organic layer was washed once with brine.
The organic layer was distilled to recover toluene as well as 2,6,6,7,8,8-hexamethyl-2,3-dihydroindano[4,5-b]furan (Bp 124°C at 4 mm Hg).
The nmr spectrum of 2,6,6,7,8,8-hexamethyl-2,3-dihydroindano[4,5-b]furan was as follows: 1.21-1.68 ppm (ms, 18H), 2.07 ppm (q, 1H), 2.92 ppm (ddd, 1H), 3.41 ppm (ddd, 1H), 5.01-5.16 ppm (m, 1H), 6.75 ppm (d,!H), 7.07 ppm (d,lH).
Example 8
Preparation of 7,7,8.9.9-pentamethvl-3-f2-methvlprop-2-envnbicvclof4.3.0]nonan-2-
one
Lithium diisopropylamide 1L (2.0 M in THF) was cooled to -10°C. 7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one, 320g (1.50 mole) was added dropwise over 2hrs. The reaction mass was aged 2 hours at room temperature then hexamethylphosporamide available from Aldrich Chemicals, (HMPA), 5.37g (2 mole %), sodium iodide, 4.50g (2 mole %) and methallyl chloride, 150g (1.60 mole) were added over 2hrs. The reaction mass was heated to reflux for 8 hours. The mixture was cooled to room temperature and quenched with water, 450g. The aqueous layer was separated then discarded. The organic layer was washed with brine.
The organic layer was distilled to recover THF as well as 384g of 7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-one( Bp 110°C at 2 mm Hg).
The nmr spectrum of 7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-one is as follows: 0.68-1.25 ppm (ms,15H), 1.30-1.87 ppm (m, 6H), 2.03-2.18 ppm (m, 2H), 2.61 ppm (bd, 1H), 4.58-4.73 ppm (m, 2H).
Example 9
Preparation of 7J.8.9.9-pentamethvl-3-(2-methvlprop-2-envnbicvcIo[4.3.01nonan-2-ol
7,7,8,9,9-Pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-one, 140g (0.53 mole) in toluene (60g) was fed into RED-AL® (available from Aldrich Chemicals) (65% in toluene) 23 Ig (0.74 mole) at room temperature over 3hrs. The reaction mass was quenched with aqueous caustic soda (147 g of 20% NaOH). The mass was heated to 65 °C then water (500 ml) was added. The aqueous layer was separated and extracted once with toluene (86 g). The combined organic layers were dried over sodium sulfate.
The organic layer was distilled to recover toluene as well as 7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-ol as a mixture of isomers (Bp 132-133°C at 3 mmHg).
The nmr spectrum of 7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-ol is as follows: 0.61-1.02 ppm (ms, 15H), 1.05-1.56 ppm (m, 6H), 1.71-1.88 ppm (m,4H), 1.95-2.54 ppm (m,2H), 3.25-3.96 ppm (m,lH), 4.67-4.80 ppm (m, 2H).
Example 10
Preparation of 4.4.10.10)1.12.12-heptamethvl-3-oxatricvclo [7.3.0.01dodecane
Asolutionof7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-ol, 2.31g (8.8 millimole), methanesulfonic acid, 0.04g (0.4 millimole), and 1-nitropropane 2.3 Ig was stirred for 24hrs at room temperature. The reaction mass was neutralized with aqueous sodium carbonate (10% solution). The aqueous layer was separated and discarded. The organic layer was concentrated on a rotary evaporator.
Distillation provided 4,4,10,10,1 l,12,12-heptamethyl-3-oxatricyclo[7.3.0.0]-dodecane as a mixture of isomers (Bp 98°C at 2 mm Hg).
The nmr spectrum of 4,4,10,10,11,12,12-heptamethyl-3-oxatricyclo[7.3.0.0]dodecane was as follows: 0.61-1.27 ppm (ms, 21H), 1.32-1.85 ppm (m, 6H), 2.45-2.61 ppm (m, 1H) -.92-3.98 ppm (m, 1H).
Example 11
Preparation of IJ.ZJJ-pentamethvl-S-(2-methvlprop-l-envnI)2,3,5,6,7
pentahvdroinden-4-one
A solution of CASHMERAN® (IFF) 400g (1.94 mole) and THF (200 milliliter) was fed into lithium diisopropylamide 1L (2.0 M in THF) at -10°C. The reaction mass was aged for 2 hours and allowed to warm to 0°C. Methallyl chloride 248g (2.7 mole) was added over 2 hours. The reaction was warmed to room temperature, then heated to 60°C for 20 hours. The mixture was cooled and quenched with 10% hydrochloric acid (1 liter). The crude mass was washed with brine.
The organic layer was distilled to recover THF and 310g of l,l,2,3,3-pentamethyl-5-(2-methylprop-2-enyl)-2,3,5,6,7-pentahydroinden-4-one (Bp 142-143°C at 2 mm Hg).
The nmr spectrum of l,l,2,3,3-pentamethyl-5-(2-methylprop-2-enyl)-2,3,5,6,7-pentahydroinden-4-one is as follows: 0.86-1.23 ppm (ms,15H), 1.36-1.66 ppm (m, 2H), 1.72 ppm (bs, 3H), 1.75-2.39 ppm (m, 4H), 2.59-2.71 pprn (m,lH), 4.70 ppm (d, 2H).
Example 12
Preparation of 3-(2-bromoethvn-7J.8.9.9-pentamethvIbicvcIof4.3.01nonan-2-one
A solution of 7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one 200g (0.97 mole) and THF (lOOmL) is fed into lithium diisopropylamide 1L (1.0 M in THF) and HMPA (lOg 5 mole percent) at -30°C. The reaction mass is aged for 2 hours and allowed to warm to 0°C. 1,2-
Dibromoethane 200g (1.06 mole) is added over 2 hours. The reaction is warmed to room temperature and aged for 24hrs. The mixture is quenched with 10% hydrochloric acid (200mL). The crude mass is washed with brine.
Distillation would provide 3-(2-bromoethyl)-7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one as a mixture of isomers.
Example 13
Preparation of 3-f2-bromoethvlV7.7.8.9.9-pentamethvlbicyclof4.3.01nonan-2-ol
A solution of 3-(2-bromoethyl)-7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one, 200g (0.63 mole) in toluene (60 g) is fed into RED-AL® (65% in toluene) 218g (0.70 mole) at 60°C in Ihr. The reaction mass is quenched with aqueous caustic soda (200 g of 50% NaOH) at 60°C. The mass is diluted with water (500 ml) and cooled to room temperature. The aqueous layer is separated and discarded.
Distillation would provide 3-(2-bromoethyl)-7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-ol as a mixture of isomers.
Example 14
Preparation of 10,10,11 J2.12-Dentamethyl-3-oxatricvcIo f7.3.0.01dodecane
A solution of 3-(2-bromoethyl)-7,7,8)9,9-pentamethylbicyclo[4.3.0]nonan-2-ol, 50g (0.16 mole) and THF (100 ml) is fed into sodium hydride 6.4g (60% dispersion in mineral oil) and THF (300 ml) at room temperature. The reaction mass is heated to reflux for 8 hours and cooled to room temperature. The reaction mass is quenched with brine (100 ml). The aqueous layer is separated and discarded.
Distillation would provide 10,10,ll,12,12-pentamethyl-3-oxatricyclo[7.3.0.0]-
Hnrlpnnnft us n tniYtiirp nf isnmprs
dodecane as a mixture of isomers.
Example 15
A fragrance was prepared according to the following formulation:

(Table Removed)
This fragrance was described as having a citrus odor.
(Table Removed)
Example 16
The following materials made in the above examples were described as having the following fragrance characteristics:
(Table Removed)

We Claim:
1. A polyalkylcyclic compound of formula (I) having the structure:
(Strucrure Removed)
where

or A and B together form the ring structure
(Strucrure Removed)
and X, R' and R are independently H and CH3 and m=0 or 1 and wherein the dotted line optionally represents a part of double bond.
2. A polyalkylcyclic compound as claimed in claim 1, wherein the compound is selected from 4,10,10,11,12,12-hexamethyl-3-oxatricyclo [7.3.0.0]dodecane and its isomers.
3. A polyalkylcyclic compound as claimed in claim 1, wherein the compound is 4,4,10,10,11,12,12-heptamethyl-3-oxatricyclo[7.3.0.0]dodecane.
4. A polyalkylcyclic compound as claimed in claim 1, wherein when m=0, the compound is
(Strucrure Removed)
5. A polyalkylcyclic compound as claimed in claim 1, wherein when m=l, the
compound is
(Strucrure Removed)
6. A polyalkylcyclic compound as claimed in claim 1, wherein A and B together
form a ring structure to provide a compound with the structure:
(Strucrure Removed)
where X is CH3, R and R' are independently H and CH3 and m=0.
7. A process for the preparation of polyalkylcyclic compounds of formula (I) as claimed in claim 1 having the structure:
(Strucrure Removed)
wherein dotted lines optionally represents a part of the double bond; M=0 or 1; A=O; B is CH3C(=CH2)CH2-,CH2=CHCH2-, BrCH2CH2- or BrCH(CH3)CH2; A and B together is -CH2C(RR')-O- (R and R' are independently represented by H or CH3) and X is also independently represented by H or CH3; the said process comprising the steps of: (a) reacting a compound of general formula (II) by stirring with lithium di-isopropyl amide and at a temperature range of -10°C to ambient temperature in an organic solvent for a period of 2-4 hours,
(Strucrure Removed)
wherein dotted line, M and X have the same definition mentioned above;
(b) treating the reaction mixture of step (a) with HMPA, optionally sodium
iodide and substituted or unsubstituted unsaturated alkyl halide or
saturated 1,2-dihaloalkane at an ambient temperature to reflux temperature
for a period of 8-24 hrs. to obtain compounds of formula (III)
(Formula Removed)
wherein dotted line, B, M and X have the same definition as mentioned above;
(c) reducing the compound of formula (III) of step (b) with 70% sodium
bis(2-methoxyethoxy)aluminium hydride solution in toluene or 65%
sodium bis(2-methoxyethoxy)aluminium hydride solution in toluene at a
temperature range of 60°-100°C for a period of 1 to 4 hours to obtain
compound of formula (IV)
(Formula Removed)
wherein dotted line, B, M and X have the same definition as mentioned above;
(d) treating the compound of step (c) of formula [IV, B= CH3C(=CH2)CH2-] with methanesulphonic acid, in an organic solvent at a temperature range of ambient to 90°C for a period of 15-24 hrs. or formula [IV, B=BrCH2CH2-] with sodium hydride in an organic solvent at reflux temperature for a period of 6-10 hrs to obtain compounds of formula (IA)
(Formula Removed)
wherein dotted line, M, R, R' and X represent the same definition as mentioned above.